race to the Second Edition Preface to the First Edition 'kno\t'ledgements Contents

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1 Contents race to the Second Edition Preface to the First Edition 'kno\t'ledgements Chemistry and Basic Intermediates. Introduction. Basic Chemistry Basic Structure of a Polyurethane Elastomer. Synthesis of Basic Urethane Building Blocks. Isocyanates. Storage Life and Reactions of Isocyanates with Themselves-Dimers (Uretidinediones) Uretidiones Polyols. Polyesters. Polyethers. Chain Extenders and Crosslinking Agents Catalvsts 2. Polyurethane Elastomer Chemistry. Liquid Processing Routes Millable Elastomer Synthesis. Thermoplastic Linear Urethane Elastomers. Concept of Equivalent Weights Concept of the Complete Urethane Chemical System Polyol Quantization by Chemical Analysis. Other Isocyanate Analytical Terms Other Useful Terms Example Calculation for a Typical Polyurethane Elastomer Synthesis Blends Calculation of Isocyanate Proportions for a Water Blow Foam System. Plfp{"t m Flpyihl" to Rigid Segment on Urethane Prooerties. XI

2 CONTENTS 3. Property-Structure Relationships in Polyurethanes Introduction. Flexible Segments. Polyethers Polycaprolactones. Rigid Segments Aliphatic Versus Aromatic Diisocyanates Aliphatic Diisocyanates and Transparency Effect of Diisocyanate Structure on the Relative Thermal Stability of Polyurethane Elastomers Chain Extension of Unsymmetrical Diisocyanates. Glycols. Chain Extension of Symmetrical Diisocyanates with Diols Synthesis. Even Molar Ratio Effects Influence of the Diol Structure on Thermal Stability of the PU Elastomer: Molar Ratios 1:2:1. Loss Tangent Values and Chain Extender Composition. Uneven Molar Ratio Effects with Respect to the Diisocyanate Comparison of the Thermal Stability Effects of a Diamine with Dibls (as Chain Extenders) in Polyurethane Elastomers (Molar Ratio 1 :3: 2) Differential Scanning Calorimetry (DSC) as a Means of Predicting Thermal Stability (Molar Ratio 1:2:1) DSCStudies and the Molar Ratio 1:2.6:1... DSC as a Means of Predicting the Relative Thermal Stability of a Diamine (Polacure) with Diol Chain Extenders Contribution of Crosslinks to Properties Crosslinking and Thermal Stability in Polyurethane Elastomers. Synthesis Technique In-Situ Isocyanate and Isocyanurate Crosslinking. PU Elastomer Compositions... Influence of% Free NCO on the Properties of the PU Elastomer at Room Temperature Strength Properties at Elevated Temperature. Dynamic Mechanical Thermal Analysis (DMT A). Thermal Equilibrium Properties Low Temperature Stiffening and Glass Transition Temperature (T a) Hazards. Thermal Stability and Cros~link Structure in PUs. Structure in Polyurethane Elastomers Continued Crystal Growth Plasticization. 4. Reaction Rates, Catalysis and Surfactant Reaction Rates Diisocyanates Polyols. Tpmnpr"hlrp

3 CONTENTS xv Catalysis. Acid Catalysis and Prepolymer Stability (Shelf Life) Shelf Life Stability of Prepolymers Base Catalysis Additional Comments on RIM Catalysis. Tertiary Amines. Organometallic and Other Metal Compounds Catalyst Combinations Surfactants (Surface Active Agents) Ionic Surfactants. Non-ionic Surfactants. 5. Liquid Polyurethane Elastomer Systems. Stable Prepolymer Systems Simple Hand Casting Procedure. Chain Ext~nders. Processing of TDI Prepolymers. Processing Variables. Type of Curative. Reaction Temperature Other Representative Polymer Systems Unstable Prepolymer System. Water Crosslinked Millable Vulkollan for Compression Moulding Cellular Polyurethane Elastomers. Vulkollan System Cellular Urethanes from Stable Prepolymers Solvents Compression Moulding of Cast Elastomers. Spray Application of Urethane Elastomers Note on Water Content of Polypols of Urethane Elastomers. Alternative Chain Extenders to MOCA. 3,3'-Dimethyl-4,4'-diaminodicyclohexylmethane. Diols as Chain Extenders... Synthesis and Properties of Polyurethane Elastomers Based on Aromatic Versus Aliphatic Diisocyanates CHDI Prepolymer Synthesis and Chain Extension. PPDI Prepolymer Synthesi~ and Chain Extension. 6. Reaction Injection Moulding (Liquid Injection Moulding) The Process RIM Formulation. Water. Physical Properties of RIM Urethane Systems RIM Machine Design Energy Requirements of RIM. Mechanism of Impingement Mixing Mould Design. Transition Zone. 11'

4 CONTENTS xv Catalysis. Acid Catalysis and Prepolymer Stability (Shelf Life) Shelf Life Stability of Prepolymers Base Catalysis Additional Comments on RIM Catalysis. Tertiary Amines. Organometallic and Other Metal Compounds Catalyst Combinations Surfactants (Surface Active Agents) Ionic Surfactants. Non-ionic Surfactant.!;..Liquid Polyurethane Elastomer Systems. Stable Prepolymer Systems Simple Hand Casting Procedure. Chain Extenders. Processing of TDI Prepolymers. Processing Variables. Type of Curative. Reaction Temperature Other Representative Polymer Systems Unstable Prepolymer System. Water Crosslinked Millable Vulkollan for Compression Moulding Cellular Polyurethane Elastomers. Vulkollan System Cellular Urethanes from Stable Prepolymers Solvents Compression Moulding of Cast Elastomers. Spray Application of Urethane Elastomers.. Note on Water Content of Polypols of Urethane Elastomers. Alternative Chain Extenders to MOCA. 3,3'-Dimethyl-4,4'-diaminodicyclohexylmethane. Diols as Chain Extenders. Synthesis and Properties of Polyurethane Elastomers Based on Aromatic Versus Aliphatic Diisocyanates CHDI Prepolymer Synthesis and Chain Extension. PPDI Prepolvmer Synthesis and Chain Exten~inn 6. Reaction Injection Moulding (Liquid Injection Moulding) The Process RIM Formulation. Water. Physical Properties of RIM Urethane Systems RIM Machine Design Energy Requirements of RIM. Mechanism of Impingement Mixing Mould Design. Tr"n~;t;"n 7"np ? ton

5 XVI CONTENTS Moulding Ribs and Radius. Runners Mould Sealing Processing Economics Reinforced Reaction Injection Moulding Dispersion of Fibre Reinforcement Machinery \ 7. Milia ble Polyurethane Elastomers. Sulphur Vulcanized Grades Millable Poly~ther Polyurethane Elastomers. Plasticization ~ Filler Reinforcement Isocyanate-Cured Urethane Rubber Peroxide-Cured Polyurethane Elastomers Cure Temperature Effect of Fillers. Combined Peroxide and Diisocvanate Cures. 8. Polyurethane Adhesives Reasons for Adhesive Properties of Polyurethane and Diisocyanate-Based Adhesives. Isocyanate Reactivity. Self Polymerization Surface Wetting Properties. Polarity Graded Physical Properties. Reaction with Unreactive Surfaces Reasons for the Apparent Universal Applications of Polyurethanes as Adhesives.. Methods of Using Isocyanates as Adhesives. As an Isocyanate Primer.. By In-Situ Polyurethane Polymerization As Polyurethane Elastomer Without. or With Added Polyisocyanates Thermoplastic Polyurethane Elastomer Types Elastomer Gum Types Blocked Di- or Polyisocyanate Adhesives Aqueous Dispersions of Polyurethanes. Film and Tape Polyurethane Adhesives. Powdered Polyurethane. Stabilization of Adhesives 9. Thermoplastic (Linear Polyurethane Elastomers). Partially Crosslinked Thermoplastic Polyurethanes Synthesis of Thermoplastic Polyurethane Preparation. Notes on Large-Scale Production Synthesis Procedures Processin~ of ThermonlHst.ic Polvllret.hH.nes

6 r()ntfnt~ XVII Extrusion Injection Moulding Calendering Hot-Melt Calendering. Film Lamination Solution Applications Reactive Coatings. loo%-solids Reactive Systems. Commercially Available TPUs Comment About the Set Properties of TPUs. Microporous Thermoplastic Polyurethanes Blends Processing of Transparent Thermoplastic Polyurethane Elastomer by Injection Moulding. Thermoplastic Polyurethane Elastomers as Hydraulic Seal Materials CHDI-Based Polyurethanes. Polyester TPUs. Mixed Aliphatic Oiols as Chain Extenders (CHOM and BOO). Polyether TPUs. Thermal Stability. Polycaprolactone/CHDI Polyurethanes Polycaprolactone/pPDI Polyurethanes Polyether/PPDI Polyurethanes. Polyether/CHDI Polyurethanes. Energy Absorption (tan 15). Post-Cure Prediction Responses. r()nchl~i()n~ Water Dispersions of Polyurethane Elastomers. Self-Emulsifying Latex. Emulsified Latex Polyurethane Ionomers. Special Features of Water-Dispersed Polyurethane Elastomers Anionic Dispersions "00 Cationic Dispersions. Practical Example for the Preparation of a Polyurethane Dispersion (Melt-Dispersion Technique). 290 I. Analysis and Characterization of Polyurethane Elastomers Diisocyanates. Measurement of NCO Content. Total Chlorine: Principle of the ASTM Method D1638 Acidity Hydrolyzable Chlorine Isomer Ratio Activity of Diisocyanate Diisocyanates in the Atmosphere Polyol Analysis im

7 CONTENT Hydroxyl Number Primary and Secondary Hydroxyl Groups. Water Content Acid Number Measurement of ph (Apparent). Hydrolytic Stability Unsaturation Peroxide Content General Analytical Parameters for Polyols. Infrared Spectroscopy Techniques. Determination of Isomer Ratio of TDI by Infrared Spectroscopy Determination of Unreacted NCO Groups in a Polyurethane Elastomer An Additional Rapid Infrared Method for the Quantitative Analysis of NCO Present in a Polyurethane Elastomer Chromatography Techniques. Gas-Liquid Chromatography Thin Layer Liquid Chromatography. Thermal Analysis. Identification of the Components in a Polyurethane Polyesters Polyethers. Differentiation of Polymers Present in a Polyurethane.... General Analysis of Miscellaneous Elements in a Polyurethane Elastomer Colour Reactions for Polyurethane Identification References 12. Special Types of Polyurethane Elastomers Hydroxy- Terminated Polybutadienes Process Oils and Plasticizers Low- Temperature Resistance Transparent Polyurethane Elastomers Amine- Terminated Polyols. Fluorinated Polyolls. uv Light Curable PU Systems. 13. Properties and Applications. Tensile Properties. In Tension. In Compression. Load Deflection Properties Comparison of Physical Properties of Polyurethane Elastomers with Common Rubbers and Plastics Energy Absorption Properties Wear Resistance. Friction Properties Environmental and Ageing Properties Light Resistance. High Energy Radiation Effects. Electrical Properties

8 :ONTENTS XIX Applications. Current Types of PU Elastomer Solid Tyres. Pneumatic Polyurethane Tyres Microcellular Shoe Solings. Blends of TPU with other Thermoplastics Rollers Automotive Body Panels and Bumpers Rain-Erosion Protection of Surfaces. Cold-Curing Elastomers Low-Speed Tyre-Filling Compositions Water Vapour Permeable PU Elastomers Polyurethane Elastomers in Medicine Millable Polyl;1rethane Elastomers. Fillers for Cold-Cast Polyurethane Plasticizers for Polyurethane Elastomers Manufacturing Factors. Moulding Shrinkage Mould Lubricant Mould Cleaning. Machining 'n.' Health Hazards and Precautions Toluene Diisocyanate (TDI) 409 Diphenylmethane Diisocyanate (MDI) 409 1,5-Naphthalene Diisocyanate (NDI) Toxicity Data for the Analogues Aromatic and Aliphatic Diisocyanates 411 General Toxicity Problems..413 Handling Isocyanates and Manufacture of Polyurethane Products Skin Irritation Protective Clothing. 416 First Aid 416 Specific Hazards Associated with the Manufacturing Processes Urethane Rubbers. 417 Manufacture of Moulded Articles Surface Coatings..418 Printing Inks Adhesives Isocyanate Monitoring and Detection. 420 Analytical Monitoring Techniques Alternative Method Determination of TDI in Solvent Atmosphere Diamines 425 Polyols and Glycols. 425 Waste Disposal. 426 References and Bibliography Inde~, 0.429

A Glossary of Terms Used in the Adhesives, Coatings and Elastomers (ACE) Sector

A Glossary of Terms Used in the Adhesives, Coatings and Elastomers (ACE) Sector Abrasion resistance The ability of the coating membrane to resist mechanical action such as foot traffic and particles, which